CN103772566A - Nitrogen-containing functionalized rare-earth syndiotactic polystyrene and preparation method thereof - Google Patents
Nitrogen-containing functionalized rare-earth syndiotactic polystyrene and preparation method thereof Download PDFInfo
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- CN103772566A CN103772566A CN201410064315.2A CN201410064315A CN103772566A CN 103772566 A CN103772566 A CN 103772566A CN 201410064315 A CN201410064315 A CN 201410064315A CN 103772566 A CN103772566 A CN 103772566A
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Abstract
The invention discloses nitrogen-containing functionalized rare-earth syndiotactic polystyrene and a preparation method thereof. The weight average molecular weight of the nitrogen-containing functionalized rare-earth syndiotactic polystyrene is 1*10<4>-120*10<4>; the syndiotactic degree of the nitrogen-containing functionalized rare-earth syndiotactic polystyrene is not less than 90% in terms of the overall mass percent 100% of a polymer; a monomer is selected from a styrene ramification which contains a nitrogen substituent group and at least contains a tertiary amine group substituent group; the substituent group can be directly connected to the ortho-position, meta-position or para-position of styrene and can also be directly connected to alkyl positioned on the ortho-position, meta-position or para-position of the styrene; the styrene ramification can contain a single substituent group, double substituent groups or three substituent groups, and the substituent groups can be the same or different.
Description
Technical field
The invention belongs to functional high molecule material technical field, relate to nitrogenous functional rare earth syndiotactic polystyrene of a class and preparation method thereof.
Background technology
Since Ishihara adopted metallocene catalyst successfully to synthesize first syndiotactic polystyrene (sPS) in 1985, because sPS fusing point is up to 270 ℃ and have than complete same polystyrene (iPS) crystallization velocity faster, therefore sPS is more and more subject to people's attention, and applies more and more extensive.Functionalization is to realize the effective means of macromolecular material high performance, and general purpose polystyrene (GPPS) has successfully been prepared functional polyalkylene vinylbenzene by introducing functional groups, has effectively improved the performance of GPPS.The functionalization of syndiotactic polystyrene is the important research direction of field of polymer technology always, and development functionality syndiotactic polystyrene will be expanded the Application Areas of sPS effectively.
Summary of the invention
Nitrogen-containing group is very easily prepared effective catalyst with the precious metal complexing such as gold (Au), silver (Ag), platinum (Pt), and nitrogen-containing group is also very easily prepared amphipathic nature material with hydroxyl complexing, or prepares efficient electro-conductive material by hydroxyls a large amount of on carbon black.Polystyrene is a kind of important polymer carrier, and syndiotactic polystyrene will greatly improve physical and mechanical properties and the heat resisting temperature of polystyrene, therefore, develops nitrogenous functional syndiotactic polystyrene and has great importance.Compared with the transition metal using with metallocene catalyst, rare earth metal has 3 constant valence states, without variation of valence, polymerization product ageing-resistant performance is good, needn't deviate from ash content, rare earth catalyst activity is high, and structure direction is good, and Given this present invention adopts rare earth catalyst to prepare nitrogenous functional syndiotactic polystyrene.
Nitrogenous functional rare earth syndiotactic polystyrene provided by the present invention has following feature: the weight-average molecular weight general range of nitrogenous functional rare earth syndiotactic polystyrene is 1 × 10
4-120 × 10
4, preferable range is 5 × 10
4-80 × 10
4; By polymkeric substance total amount mass percent 100%, nitrogenous functional rare earth syndiotactic polystyrene, normality is not less than 90% therebetween.The monomer that nitrogenous functional rare earth syndiotactic polystyrene adopts is selected from nitrogenous substituent styrene derivatives, and at least contains a tertiary amine group substituting group; Substituting group can directly be connected in cinnamic ortho position, a position or contraposition, also can be connected to above the alkyl in vinylbenzene ortho position, a position or contraposition; Above-mentioned styrene derivatives can contain monosubstituted base, disubstituted or three substituting groups; The substituting group containing on disubstituted, three substituting group styrene derivativess can be identical, also can different (that is: nitrogen-containing hetero substituting group styrene derivatives).Nitrogenous styrene derivatives is generally selected from N, N-dialkyl amino vinylbenzene, N, N-diaryl amido vinylbenzene; More preferably from N, N-dimethyl amido vinylbenzene, N, N-diethyl amido vinylbenzene, N, N-di-t-butyl amido vinylbenzene, N, N-phenylbenzene amido vinylbenzene; Most preferably certainly to N, N-dimethyl amido vinylbenzene (that is: 4-ethenylphenyl dimethyl amine), to N, N-diethyl amido vinylbenzene (that is: 4-ethenylphenyl diethylamide), to N, N-di-t-butyl amido vinylbenzene (that is: 4-ethenylphenyl di-t-butyl amine), to N, N-phenylbenzene amido vinylbenzene (that is: 4-ethenylphenyl diphenylamine).
The rare earth catalyst of the nitrogenous functional rare earth syndiotactic polystyrene of preparation provided by the present invention is made up of A and two parts of B:
A is rare earth compounding CpLnR
2x
n, structural formula is as follows, wherein: Cp is cyclopentadienyl ligand C
5(R
1) (R
2) (R
3) (R
4) (R
5), Ln is rare earth metal, R is the alkyl being directly connected with rare earth metal, X be with rare earth metal on coordinating group.Ln is generally selected from Nd, Sc, Y, Lu, Gd, Sm, more preferably from Sc, Y, Lu, preferably from Sc.R is generally selected from CH
2siMe
3, CH
2c
6h
4nMe
2-o, CH
2ph, CH
2cH=CH
2, 1,3-C
3h
4(Me), 1,3-C
3h
3(SiMe
3)
2, CH (SiMe
3)
2, CH
3, CH
2cH
3,
i-Pr,
t-bu, more preferably from CH
2siMe
3, CH
2c
6h
4nMe
2-o, CH
2ph, CH
2cH=CH
2; Most preferably from CH
2siMe
3, CH
2c
6h
4nMe
2-o, wherein Ph is that phenyl, Me are that methyl, Pr are that propyl group, Bu are butyl.R
1, R
2, R
3, R
4, R
5generally be selected from H, CH
3, CH
2cH
3,
i-Pr,
t-Bu, Ph, CH
2ph, SiMe
3, CH
2siMe
3, wherein Ph is that phenyl, Me are that methyl, Pr are that propyl group, Bu are butyl, R
1, R
2, R
3, R
4, R
5can be the same or different; Cyclopentadienyl ligand Cp is generally selected from C
5h
5, C
5me
5, C
5me
4siMe
3, C
5hMe
4, C
5h
2me
3, C
5me
3(SiMe
3)
2, C
5h
3(SiMe
3)
2, C
5ph
5, preferably from C
5me
4siMe
3.X is Lewis acid, is generally selected from and contains O, N, the heteroatomic Lewis acid of P, S, and more preferably, from containing the heteroatomic Lewis acid of O, N, preferably, from tetrahydrofuran (THF) (THF), n is lewis acidic number, is selected from 0 or 1.
Rare earth compounding CpLnR
2x
nstructural formula
B is organoboron reagent, is generally selected from [Ph
3c] [B (C
6f
5)
4], [PhMe
2nH] [B (C
6f
5)
4], B (C
6f
5)
3in one or more mixture, preferably from [Ph
3c] [B (C
6f
5)
4].
A kind of preparation method who prepares nitrogenous functional rare earth syndiotactic polystyrene provided by the present invention is as follows: under inert nitrogen gas or argon shield, in the polymerization reactor of dry deoxygenation, add organic solvent and above-mentioned nitrogenous substituent styrene derivatives monomer by proportioning, monomer concentration is 2-50g/100mL, then add above-mentioned prepared rare earth catalyst, rare earth catalyst consumption is that the mol ratio (M/Ln) of monomer/Ln is 50-4000, reacts 0.5h to 12h at 0 ℃-80 ℃; Adopt traditional post-treating method to be dried polymkeric substance, obtain nitrogenous functional rare earth syndiotactic polystyrene.Polyreaction can have solvent exist under carry out, also can in solvent-free situation, carry out mass polymerization.In the time adopting solution polymerization mode, organic solvent is selected from saturated alkane, the mixture of one or more in aromatic hydrocarbons, chlorinated aromatic hydrocarbons, naphthenic hydrocarbon, generally be selected from normal hexane, hexanaphthene, normal heptane, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, preferably from normal hexane, hexanaphthene, toluene, chlorobenzene.
With carbon-13 nmr spectra (
13c-NMR) detect nitrogenous functional rare earth syndiotactic polystyrene between normality (mass percent, %), with gel permeation chromatograph (GPC, 145 ℃, trichlorobenzene is solvent) measure the molecular weight and molecualr weight distribution index ratio of number-average molecular weight (weight-average molecular weight with) of polymkeric substance, measure the second-order transition temperature (T of polymkeric substance with differential scanning calorimetry instrument (DSC)
g) and fusing point (T
m).
Embodiment
The present invention proposes following examples as further instruction, but and the scope of unrestricted the claims in the present invention protection.
Embodiment 1, trialkyl scandium title complex Sc (CH
2siMe
3)
3(THF)
2preparation:
In glove box, take 2.2695g ScCl
3(15mmol) put into the Schlenk bottle that fills magnetic stir bar, add 50mL tetrahydrofuran (THF).After airtight Schlenk bottle, Schlenk bottle is taken out to glove box and stir and spend the night at 80 ℃.By the ScCl after activation
3(THF)
3white suspension is taken in glove box, takes 4.2336g LiCH
2siMe
3(45mmol) dissolve with 15mL tetrahydrofuran (THF), be added drop-wise to slowly ScCl
3(THF)
3in white suspension, reaction 30min.Then, solvent THF is taken in decompression away, adds 60mL n-hexane extraction, goes out to take advantage of cold filtration after by product by freezing extraction liquid, finally the normal hexane in filtrate is taken away and is obtained 4.4557g white powder Sc (CH
2siMe
3)
3(THF)
2.
Embodiment 2, Dan Maoshuan alkyl scandium title complex (C
5hMe
4) Sc (CH
2siMe
3) preparation (THF):
In glove box, take 3.2681g Sc (CH
2siMe
3)
3(THF)
2(7.25mmol) put into the 100mL round-bottomed flask that fills magnetic stir bar, add the normal hexane dissolution with solvents of 5mL.Take 0.8862g tetramethyl-ring pentadiene (7.25mmol), with after 1mL n-hexane dissolution, under room temperature, be added drop-wise in reaction flask.After stirring at room temperature 3h, decompression concentrated solution, to 1mL left and right, is put into-35 ℃ of refrigerator overnight, and recrystallization obtains 2.2302g clear crystal (C
5hMe
4) Sc (CH
2siMe
3) (THF).
Embodiment 3, Dan Maoshuan alkyl scandium title complex (C
5me
5) Sc (CH
2siMe
3) preparation (THF):
In glove box, take 3.2681g Sc (CH
2siMe
3)
3(THF)
2(7.25mmol) put into the 100mL Schlenk bottle that fills magnetic stir bar, add the normal hexane dissolution with solvents of 5mL.Take 0.9880g pentamethyl-cyclopentadiene (7.25mmol), with after 1mL n-hexane dissolution, under room temperature, be added drop-wise in reaction flask.Schlenk bottle is taken out after glove box after 50 ℃ of stirring reaction 48h, and decompression concentrated solution, to 1mL left and right, is put into-35 ℃ of refrigerator overnight, and recrystallization obtains 2.0021g clear crystal (C
5me
5) Sc (CH
2siMe
3) (THF).
Embodiment 4, Dan Maoshuan alkyl scandium title complex (C
5me
4siMe
3) Sc (CH
2siMe
3) preparation (THF):
In glove box, take 3.2681g Sc (CH
2siMe
3)
3(THF)
2(7.25mmol) put into the 100mL round-bottomed flask that fills magnetic stir bar, add the normal hexane dissolution with solvents of 10mL.Take the trimethyl silicon based tetramethyl-ring pentadiene of 1.4092g C
5me
4h (SiMe
3) (7.25mmol), with after 1mL n-hexane dissolution, under room temperature, be added drop-wise in reaction flask.After stirring at room temperature 2h, decompression concentrated solution, to 1mL left and right, is put into-35 ℃ of refrigerator overnight, and recrystallization obtains 2.7389g clear crystal (C
5me
4siMe
3) Sc (CH
2siMe
3) (THF).
Embodiment 5, Dan Maoshuan alkyl scandium title complex (C
5me
4c
6h
4oMe-o) Sc (CH
2siMe
3)
2preparation:
In glove box, take 0.0760g ScCl
3(0.5mmol) put into the 100mL Schlenk bottle that fills magnetic stir bar, add and airtightly after 10mL tetrahydrofuran (THF) take out 80 ℃ of stirrings of glove box and spend the night, then by the ScCl after activation
3(THF)
3white suspension is taken in glove box.In glove box by C
5me
4h (C
6h
4oMe-o) react the 0.1330g[C making with KH
5me
4(C
6h
4oMe-o)] K (0.50mmol) adds after 5mL tetrahydrofuran (THF), is slowly added drop-wise to ScCl under room temperature
3(THF)
3room temperature reaction 1h in tetrahydrofuran (THF) suspension.0.094g Me
3siCH
2li (1.00mmol) is slowly added drop-wise in reaction solution after adding 3mL tetrahydrofuran solution, and stirring at room temperature 30min final vacuum pumps solvent, and residue extracts with toluene.Vacuum pumps after toluene, obtains 0.1881g white micro-crystals (C with cold normal hexane solvent wash resistates
5me
4c
6h
4oMe-o) Sc (CH
2siMe
3)
2.
Embodiment 6, Dan Maoshuan alkyl scandium title complex (C
5me
4cH
2siMe
2(O) PPh
2) Sc (CH
2siMe
3)
2preparation:
In glove box, take 2.1619g methyldiphenyl base phosphine oxide (10mmol) and put into the 100mL round-bottomed flask bottle that fills magnetic stir bar, add 15mL tetrahydrofuran (THF) to be dissolved.The hexane solution (2.3mol/L) of getting 3.61mL n-BuLi with syringe dropwise joins in round-bottomed flask, and stirring at room temperature 30min obtains Ph
2p (O) CH
2the tetrahydrofuran solution of Li.Taking 2.6580g chloro-dimethyl-(2,3,4,5-tetramethyl--2,4-cyclopentadiene)-silane (12mmol) puts into the 100mLSchlenk bottle that fills magnetic stir bar, adds 15mL tetrahydrofuran (THF) to be dissolved.By Ph
2p (O) CH
2the tetrahydrofuran solution of Li dropwise joins in Schlenk bottle airtight, Schlenk bottle is taken out to 6 days final vacuums of 50 ℃ of stirring reactions of glove box and pump solvent, residue adds toluene extraction, and vacuum pumps the toluene solvant in filtrate, and residue obtains 2.9982g orange solids C with normal hexane washing again
5me
4h (SiMe
2cH
2(O) PPh
2).
Take 2.7620g Compound C obtained above
5me
4h (SiMe
2cH
2(O) PPh
2) (7mmol) put into the 100mL round-bottomed flask that fills magnetic stir bar, add 15mL tetrahydrofuran (THF) to be dissolved.By 0.7242g Me
3siCH
2li (7.7mmol) dropwise joins in round-bottomed flask after adding the dissolving of 10mL tetrahydrofuran (THF), stirring at room temperature 2h, and vacuum pumps solvent, and residue obtains 2.7480g orange solids C with normal hexane washing
5me
4(SiMe
2cH
2(O) PPh
2) Li.
In glove box, take 2.7030g Sc (CH
2siMe
3)
3(THF)
2(6mmol) put into the 100mL round-bottomed flask that fills magnetic stir bar, add 10mL tetrahydrofuran (THF) to be dissolved.Take 2.5278g[Et
3nH] [BPh
4] (6mmol) add after 10mL tetrahydrofuran (THF) and be added drop-wise in round-bottomed flask under room temperature, stirring at room temperature reaction 30min.Take 2.4030gC
5me
4(SiMe
2cH
2(O) PPh
2) Li (6mmol) add 10mL tetrahydrofuran (THF) dissolve after, be added drop-wise in round-bottomed flask, stirring at room temperature 30min, vacuum pumps solvent, residue pumps normal hexane with n-hexane extraction final vacuum.Residue is dissolved in toluene, puts into-35 ℃ of refrigerator overnight after concentrated solution, recrystallization obtains 2.3910g white crystal (C
5me
4cH
2siMe
2(O) PPh
2) Sc (CH
2siMe
3)
2.
Embodiment 7, trialkyl scandium title complex Sc (CH
2c
6h
4nMe
2-o)
3preparation:
In glove box, take 1.5134g ScCl
3(10mmol) put into the Schlenk bottle that fills magnetic stir bar, add 8mL tetrahydrofuran (THF).Take 4.2341g LiCH
2c
6h
4nMe-o (30mmol) dissolves with 14mL tetrahydrofuran (THF), is added drop-wise to ScCl
3tHF solution in, reaction 30min.Then, solvent THF is taken in decompression away, adds the extraction of 28mL toluene, after extraction liquid is concentrated, puts into-35 ℃ of refrigerator overnight crystallizations, obtains 4.2067g light yellow crystal Sc (CH
2c
6h
4nMe
2-o)
3.
Embodiment 8, Dan Maoshuan alkyl scandium title complex (C
5h
4me) Sc (CH
2c
6h
4nMe-o)
2preparation:
In glove box, take 1.7922g Sc (CH
2c
6h
4nMe-o)
3(4.00mmol) put into the 100mLSchlenk bottle that fills magnetic stir bar, add the tetrahydrofuran solvent of 12mL to dissolve.Take 0.3170g methyl cyclopentadiene (4.80mmol), after dissolving with 6mL tetrahydrofuran (THF), under room temperature, join in Schlenk bottle.To after airtight Schlenk bottle, take out after glove box after 40 ℃ of stirring reaction 2h, vacuum pumps solvent, residue n-hexane extraction, and room temperature is placed and is spent the night, and recrystallization obtains 1.2260g yellow crystals (C
5h
4me) Sc (CH
2c
6h
4nMe-o)
2.
Embodiment 9, Dan Maoshuan alkyl scandium title complex (C
5hMe
4) Sc (CH
2c
6h
4nMe-o)
2preparation:
In glove box, take 0.4770g Sc (CH
2c
6h
4nMe-o)
3(1.00mmol) put into the 100mLSchlenk bottle that fills magnetic stir bar, add the tetrahydrofuran solvent of 10mL to dissolve.Take 0.1221g tetramethyl-ring pentadiene (1.00mmol), after dissolving with 5mL tetrahydrofuran (THF), under room temperature, join in Schlenk bottle.To after airtight Schlenk bottle, take out after glove box after 70 ℃ of stirring reaction 5h, vacuum pumps solvent, and residue is with being dissolved in toluene after normal hexane washing, and concentrated toluene solution, adds a small amount of ether solvent to be settled out 0.3700g safran crystallite (C
5hMe
4) Sc (CH
2c
6h
4nMe-o)
2.
Embodiment 10, Dan Maoshuan alkyl scandium title complex (C
5me
5) Sc (CH
2c
6h
4nMe-o)
2preparation:
In glove box, take 1.5370g Sc (CH
2c
6h
4nMe-o)
3(3.45mmol) put into the 100mLSchlenk bottle that fills magnetic stir bar, add the tetrahydrofuran solvent of 10mL to dissolve.Take 0.4701g pentamethyl-cyclopentadiene (3.45mmol), after dissolving with 5mL tetrahydrofuran (THF), under room temperature, join in Schlenk bottle.To after airtight Schlenk bottle, take out after glove box after 70 ℃ of stirring reaction 12h, vacuum pumps solvent, and residue, with being dissolved in toluene after ether washing, is put into-35 ℃ of refrigerator overnight after concentrated toluene solution, and recrystallization obtains 1.2800g yellow crystals (C
5me
5) Sc (CH
2c
6h
4nMe-o)
2.
Embodiment 11, Dan Maoshuan alkyl scandium title complex (C
5me
4siMe
3) Sc (CH
2c
6h
4nMe-o)
2preparation:
In glove box, take 1.5370g Sc (CH
2c
6h
4nMe-o)
3(3.45mmol) put into the 100mLSchlenk bottle that fills magnetic stir bar, add the tetrahydrofuran solvent of 10mL to dissolve.Take 0..6711g C5Me
4h (SiMe
3) (3.45mmol), after dissolving with 5mL tetrahydrofuran (THF), under room temperature, join in Schlenk bottle.To after airtight Schlenk bottle, take out after glove box after 70 ℃ of stirring reaction 12h, vacuum pumps solvent, and residue, with being dissolved in toluene after ether washing, is put into-35 ℃ of refrigerator overnight after concentrated toluene solution, and recrystallization obtains 1.4505g yellow crystals (C
5me
4siMe
3) Sc (CH
2c
6h
4nMe-o)
2.
Embodiment 12, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
In polymerization reactor, add successively 3mL to N, the cinnamic toluene solution of N-dimethyl amido (monomer concentration is 18g/100mL), mol ratio [M]/[Sc] of monomer and rare earth catalyst is 500, keep polymerization temperature at 25 ℃, add the prepared rare earth catalyst (C of 20 μ mol above-described embodiment 11
5me
4siMe
3) Sc (CH
2c
6h
4nMe-o)
2, then add 20 μ mol organoboron reagent [Ph
3c] [B (C
6f
5)
4], open stirring, reaction 1hr, polyreaction finishes the traditional post-treating method of rear employing polymkeric substance is dried, and between obtaining, rule are poly-to N, N-dimethyl amido vinylbenzene, polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 21.5 × 10
4, molecular weight distributing index (Mw/Mn) is 1.96, and a normality is greater than 99%, and glass transition temperature Tg is 130 ℃, and fusing point Tm is 245 ℃.
Embodiment 13, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, and mol ratio [M]/[Sc] of monomer and rare earth catalyst is 250, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 15.3 × 10
4, molecular weight distributing index (Mw/Mn) is 2.13, and a normality is greater than 99%, and glass transition temperature Tg is 130 ℃, and fusing point Tm is 245 ℃.
Embodiment 14, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, and mol ratio [M]/[Sc] of monomer and rare earth catalyst is 1000, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 33.6 × 10
4, molecular weight distributing index (Mw/Mn) is 1.97, and a normality is greater than 99%, and glass transition temperature Tg is 128 ℃, and fusing point Tm is 246 ℃.
Embodiment 15, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, and mol ratio [M]/[Sc] of monomer and rare earth catalyst is 2000, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 54.6 × 10
4, molecular weight distributing index (Mw/Mn) is 1.86, and a normality is greater than 99%, and glass transition temperature Tg is 124 ℃, and fusing point Tm is 247 ℃.
Embodiment 16, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, and mol ratio [M]/[Sc] of monomer and rare earth catalyst is 4000, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 110.6 × 10
4, molecular weight distributing index (Mw/Mn) is 1.89, and a normality is greater than 99%, and glass transition temperature Tg is 140 ℃, and fusing point Tm is 251 ℃.
Embodiment 17, a rule is poly-to N, the cinnamic preparation of N-diethyl amido
Polymeric reaction condition is identical with embodiment 12, and monomer is to N, N-diethyl amido vinylbenzene, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 24.2 × 10
4, molecular weight distributing index (Mw/Mn) is 1.79, and a normality is greater than 99%, and glass transition temperature Tg is 130 ℃, and fusing point Tm is 260 ℃.
Embodiment 18, a rule is poly-to N, the cinnamic preparation of N-phenylbenzene amido
Polymeric reaction condition is identical with embodiment 12, and monomer is to N, N-phenylbenzene amido vinylbenzene, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 34.8 × 10
4, molecular weight distributing index (Mw/Mn) is 1.88, and a normality is greater than 99%, and glass transition temperature Tg is 121 ℃, and fusing point Tm is 290 ℃.
Embodiment 19, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, selects the prepared rare earth catalyst (C of above-described embodiment 4
5me
4siMe
3) Sc (CH
2siMe
3) (THF), polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 22.1 × 10
4, molecular weight distributing index (Mw/Mn) is 1.93, and a normality is greater than 99%, and glass transition temperature Tg is 126 ℃, and fusing point Tm is 248 ℃.
Embodiment 20, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, selects the prepared rare earth catalyst (C of above-described embodiment 10
5me
5) Sc (CH
2c
6h
4nMe-o)
2, polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 19.1 × 10
4, molecular weight distributing index (Mw/Mn) is 2.15, and a normality is 99%, and glass transition temperature Tg is 130 ℃, and fusing point Tm is 244 ℃.
Embodiment 21, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, selects the prepared rare earth catalyst (C of above-described embodiment 3
5me
5) Sc (CH
2siMe
3) (THF), polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 17.0 × 10
4, molecular weight distributing index (Mw/Mn) is 1.89, and a normality is greater than 99%, and glass transition temperature Tg is 124 ℃, and fusing point Tm is 240 ℃.
Embodiment 22, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, selects the prepared rare earth catalyst (C of above-described embodiment 6
5me
4cH
2siMe
2(O) PPh
2) Sc (CH
2siMe
3)
2, polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 20.4 × 10
4, molecular weight distributing index (Mw/Mn) is 2.34, and a normality is greater than 99%, and glass transition temperature Tg is 136 ℃, and fusing point Tm is 238 ℃.
Embodiment 23, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, and organoboron reagent is selected [PhMe
2nH] [B (C
6f
5)
4], polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 23.8 × 10
4, molecular weight distributing index (Mw/Mn) is 1.90, and a normality is greater than 99%, and glass transition temperature Tg is 123 ℃, and fusing point Tm is 239 ℃.
Embodiment 24, a rule is poly-to N, the cinnamic preparation of N-dimethyl amido
Polymeric reaction condition is identical with embodiment 12, and organoboron reagent is selected B (C
6f
5)
3, polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 21.0 × 10
4, molecular weight distributing index (Mw/Mn) is 1.92, and a normality is greater than 99%, and glass transition temperature Tg is 130 ℃, and fusing point Tm is 246 ℃.
Embodiment 25, a rule is poly-to N, the cinnamic preparation of N-di-t-butyl amido
Polymeric reaction condition is identical with embodiment 12, and monomer is to N, N-di-t-butyl amido vinylbenzene, and polymer architecture and results of performance analysis are as follows: weight-average molecular weight Mw is 25.7 × 10
4, molecular weight distributing index (Mw/Mn) is 1.93, and a normality is greater than 99%, and glass transition temperature Tg is 128 ℃, and fusing point Tm is 265 ℃.
Claims (13)
1. the nitrogenous functional rare earth syndiotactic styrenic of a class, is characterized in that: weight-average molecular weight is 1 × 10
4-120 × 10
4; By polymkeric substance total amount mass percent 100%, between nitrogenous functional rare earth syndiotactic polystyrene, normality is not less than 90%; The monomer that nitrogenous functional rare earth syndiotactic polystyrene adopts is selected from nitrogenous substituent styrene derivatives, and at least contain a tertiary amine group substituting group, the one in following two kinds of modes is taked in substituent connection: (1) substituting group is directly connected in cinnamic ortho position, a position or contraposition; (2) substituting group is connected to above the alkyl in vinylbenzene ortho position, a position or contraposition; Styrene derivatives contains monosubstituted base, disubstituted or three substituting groups, and substituting group is identical or different.
2. nitrogenous functional rare earth syndiotactic styrenic according to claim 1, is characterized in that: weight-average molecular weight is 5 × 10
4-80 × 10
4.
3. nitrogenous functional rare earth syndiotactic styrenic according to claim 1, is characterized in that: described styrene derivatives is selected from N, N-dialkyl amino vinylbenzene, N, N-diaryl amido vinylbenzene.
4. according to the nitrogenous functional rare earth syndiotactic styrenic described in claim 1 or 3, it is characterized in that: described styrene derivatives is selected from N N-dimethyl amido vinylbenzene, N, N-diethyl amido vinylbenzene, N, N-di-t-butyl amido vinylbenzene, N, N-phenylbenzene amido vinylbenzene.
5. according to the nitrogenous functional rare earth syndiotactic styrenic described in claim 1 or 3, it is characterized in that: described styrene derivatives is selected from N, N-dimethyl amido vinylbenzene, to N, N-diethyl amido vinylbenzene, to N, N-di-t-butyl amido vinylbenzene,
To N, N-phenylbenzene amido vinylbenzene.
6. nitrogenous functional rare earth syndiotactic styrenic according to claim 4, it is characterized in that: described styrene derivatives is selected from N N-dimethyl amido vinylbenzene, to N, N-diethyl amido vinylbenzene, to N, N-di-t-butyl amido vinylbenzene, to N, N-phenylbenzene amido vinylbenzene.
7. the preparation method of the nitrogenous functional rare earth syndiotactic styrenic described in claim 1 or 2 or 3 or 6, it is characterized in that: under inert nitrogen gas or argon shield, in the polymerization reactor of dry deoxygenation, add organic solvent and above-mentioned nitrogenous substituent styrene derivatives monomer by proportioning, organic solvent is selected from normal hexane, hexanaphthene, normal heptane, benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, the mixture of one or more of trichlorobenzene, monomer concentration is 2-50g/100mL, then add rare earth catalyst, rare earth catalyst consumption is that the mol ratio (M/Ln) of monomer/Ln is 50-4000, at 0 ℃-80 ℃, react 0.5h to 12h, adopt traditional post-treating method to be dried polymkeric substance, obtain nitrogenous functional rare earth syndiotactic polystyrene,
Rare earth catalyst is made up of A and two parts of B: A is rare earth compounding CpLnR
2x
n, structural formula as shown in the figure, wherein: Cp is cyclopentadienyl ligand C
5(R
1) (R
2) (R
3) (R
4) (R
5), Ln is rare earth metal, is selected from Nd, Sc, Y, Lu, Gd, Sm; R is the alkyl being directly connected with rare earth metal, is selected from CH
2siMe
3, CH
2c
6h
4nMe
2-o, CH
2ph, CH
2cH=CH
2, 1,3-C
3h
4(Me), 1,3-C
3h
3(SiMe
3)
2, CH (SiMe
3)
2, CH
3, CH
2cH
3,
i-pr,
t-bu; X be with rare earth metal on coordinating group, be selected from and contain O, N, the heteroatomic Lewis acid of P, S, n is lewis acidic number, is selected from 0 or 1; R
1, R
2, R
3, R
4, R
5be selected from H, CH
3, CH
2cH
3,
i-Pr,
t-Bu, Ph, CH
2ph, SiMe
3, CH
2siMe
3, R
1, R
2, R
3, R
4, R
5can be the same or different; Cyclopentadienyl ligand Cp is selected from C
5h
5, C
5me
5, C
5me
4siMe
3, C
5hMe
4, C
5h
2me
3, C
5me
3(SiMe
3)
2, C
5h
3(SiMe
3)
2, C
5ph
5; Wherein Ph is that phenyl, Me are that methyl, Pr are that propyl group, Bu are butyl;
Rare earth compounding CpLnR
2x
nstructural formula
B is organoboron reagent, is selected from [Ph
3c] [B (C
6f
5)
4], [PhMe
2nH] [B (C
6f
5)
4], B (C
6f
5)
3in one or more mixture.
8. the preparation method of the arbitrary described nitrogenous functional rare earth syndiotactic styrenic of claim 4, it is characterized in that: under inert nitrogen gas or argon shield, in the polymerization reactor of dry deoxygenation, add organic solvent and above-mentioned nitrogenous substituent styrene derivatives monomer by proportioning, organic solvent is selected from normal hexane, hexanaphthene, normal heptane, benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, the mixture of one or more of trichlorobenzene, monomer concentration is 2-50g/100mL, then add rare earth catalyst, rare earth catalyst consumption is that the mol ratio (M/Ln) of monomer/Ln is 50-4000, at 0 ℃-80 ℃, react 0.5h to 12h, adopt traditional post-treating method to be dried polymkeric substance, obtain nitrogenous functional rare earth syndiotactic polystyrene,
Rare earth catalyst is made up of A and two parts of B: A is rare earth compounding CpLnR
2x
n, structural formula as shown in the figure, wherein: Cp is cyclopentadienyl ligand C
5(R
1) (R
2) (R
3) (R
4) (R
5), Ln is rare earth metal, is selected from Nd, Sc, Y, Lu, Gd, Sm; R is the alkyl being directly connected with rare earth metal, is selected from CH
2siMe
3, CH
2c
6h
4nMe
2-o, CH
2ph, CH
2cH=CH
2, 1,3-C
3h
4(Me), 1,3-C
3h
3(SiMe
3)
2, CH (SiMe
3)
2, CH
3, CH
2cH
3,
i-pr,
t-bu; X be with rare earth metal on coordinating group, be selected from and contain O, N, the heteroatomic Lewis acid of P, S, n is lewis acidic number, is selected from 0 or 1; R
1, R
2, R
3, R
4, R
5be selected from H, CH
3, CH
2cH
3,
i-Pr,
t-Bu, Ph, CH
2ph, SiMe
3, CH
2siMe
3, R
1, R
2, R
3, R
4, R
5can be the same or different; Cyclopentadienyl ligand Cp is selected from C
5h
5, C
5me
5, C
5me
4siMe
3, C
5hMe
4, C
5h
2me
3, C
5me
3(SiMe
3)
2, C
5h
3(SiMe
3)
2, C
5ph
5; Wherein Ph is that phenyl, Me are that methyl, Pr are that propyl group, Bu are butyl;
Rare earth compounding CpLnR
2x
nstructural formula
B is organoboron reagent, is selected from [Ph
3c] [B (C
6f
5)
4], [PhMe
2nH] [B (C
6f
5)
4], B (C
6f
5)
3in one or more mixture.
9. the preparation method of the arbitrary described nitrogenous functional rare earth syndiotactic styrenic of claim 5, it is characterized in that: under inert nitrogen gas or argon shield, in the polymerization reactor of dry deoxygenation, add organic solvent and above-mentioned nitrogenous substituent styrene derivatives monomer by proportioning, organic solvent is selected from normal hexane, hexanaphthene, normal heptane, benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, the mixture of one or more of trichlorobenzene, monomer concentration is 2-50g/100mL, then add rare earth catalyst, rare earth catalyst consumption is that the mol ratio (M/Ln) of monomer/Ln is 50-4000, at 0 ℃-80 ℃, react 0.5h to 12h, adopt traditional post-treating method to be dried polymkeric substance, obtain nitrogenous functional rare earth syndiotactic polystyrene,
Rare earth catalyst is made up of A and two parts of B: A is rare earth compounding CpLnR
2x
n, structural formula as shown in the figure, wherein: Cp is cyclopentadienyl ligand C
5(R
1) (R
2) (R
3) (R
4) (R
5), Ln is rare earth metal, is selected from Nd, Sc, Y, Lu, Gd, Sm; R is the alkyl being directly connected with rare earth metal, is selected from CH
2siMe
3, CH
2c
6h
4nMe
2-o, CH
2ph, CH
2cH=CH
2, 1,3-C
3h
4(Me), 1,3-C
3h
3(SiMe
3)
2, CH (SiMe
3)
2, CH
3, CH
2cH
3,
i-pr,
t-bu; X be with rare earth metal on coordinating group, be selected from and contain O, N, the heteroatomic Lewis acid of P, S, n is lewis acidic number, is selected from 0 or 1; R
1, R
2, R
3, R
4, R
5be selected from H, CH
3, CH
2cH
3,
i-Pr,
t-Bu, Ph, CH
2ph, SiMe
3, CH
2siMe
3, R
1, R
2, R
3, R
4, R
5can be the same or different; Cyclopentadienyl ligand Cp is selected from C
5h
5, C
5me
5, C
5me
4siMe
3, C
5hMe
4, C
5h
2me
3, C
5me
3(SiMe
3)
2, C
5h
3(SiMe
3)
2, C
5ph
5; Wherein Ph is that phenyl, Me are that methyl, Pr are that propyl group, Bu are butyl;
Rare earth compounding CpLnR
2x
nstructural formula
B is organoboron reagent, is selected from [Ph
3c] [B (C
6f
5)
4], [PhMe
2nH] [B (C
6f
5)
4], B (C
6f
5)
3in one or more mixture.
10. preparation method according to claim 7, is characterized in that: described X is selected from tetrahydrofuran (THF).
11. preparation methods according to claim 8 or claim 9, is characterized in that: described X is selected from tetrahydrofuran (THF).
12. preparation methods according to claim 7, is characterized in that: described organic solvent is hexanaphthene, normal hexane, toluene, chlorobenzene.
13. preparation methods according to claim 8 or claim 9, is characterized in that: described organic solvent is hexanaphthene, normal hexane, toluene, chlorobenzene.
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